Unsaturated esters of 10-hendecenoic acid



Patented Feb. 13, 1951 UN SATURATED ESTER-S OF IO-HENDECENOIC ACID Daniel Swern and Edmund F. Jordan, J r., Philadelphia, Pa., assignors to the United States of America. as represented by the Secretary of Agriculture No Drawing. Application September 10, 1948,

Serial No. 48,542

1 Claim.

(Granted under the act of March 3, 1883, as amended April 30, 1928; 370 0. G. 757) This application is made under the act of March 3, 1883, as amended by the act of April 30, 1928, and the invention herein described, if patented in any country, may be manufactured and used by or for the Government of the United States of America for governmental purposes throughout the world without the payment to us of any royalty thereon.

This invention relates to unsaturated esters of IO-hendecenoic acid represented by the formula CH2=CH(CH2) aCOOR wherein R is a radical selected from the group consisting of vinyl, allyl, methylallyl, chloroallyl, and furfuryl radicals, and to polymeric substances derived from these esters and has among its objects the provision of such compositions of matter and processes for their preparation. Other objects and advantages will be apparent from the following description of the invention.

We have found that vinyl IO-hendecenoate is formed on acidolysis of a vinyl ester, such as vinyl acetate, with IO-hendecenoic acid, in the presence of mercuric acetate and 100% sulfuric acid as catalyst. The allyl, chloroallyl such as 2-chloroallyl, and methyl allyl esters such as crotyl and l-methallyl esters of IO-hendecenoic acid can be prepared by direct esteriflcation of the acid with the corresponding alcohol in the presence of a suitable esterification catalyst such as naphthalenesulfonic acid, and an entraining agent, for example, benzene, adapted to remove the water formed during the reaction. Other unsaturated e ters of IO-hendecenoic acid, such as 2-methylallyl and furfuryl IO-hendecenoate are obtained by alcoholysis of methyl -hendecenoate with the appropriate alcohol, using the corresponding sodium alcoholate as catalvst.

We have further found that the tendency to polymerize displayed by unsaturated esters of IO-hendecenoic acid varies greatly depending on the nature of the oleflnic alcohol radical, and that polymers and copolymers derived from some of these esters possess properties unlike those of analogous products obtained from the corresponding esters of other monounsaturated, olefinic fatty acids.

Thus, vinyl IO-hendecenoate, when heated at 100 C. in the presence of 1% of benzoyl peroxide as catalyst, is converted Within 2 hours. to a soft, crumbly transparent gel: at 80 C. complete gelation requires approximately sixteen hours.

When the allyl or methylallyl IO-hendecenoates are heated in'the presence of 0.5% benzoyl per- 2 oxide, first for 65 hours at 50 0., then for 48 hours at 65-70 0., and finally for 24 hours at 85 C., only a small amount of the ester undergoes polymerization as evidenced by the .reduction in the iodine number of only about ten percent. Under identical conditions z-chloroallyl IO-hendecenoate is completely polymerized to a soft, transparent, pale yellow crumbly gel. The cross-linking tendencies of 2-chloroa1lyl lO-hendecenoate thus differ markedly from those of the corresponding oleate which does not form a gel even when heated for about hours at C. in the presence of 1% benzoyl peroxide.

Copolymers obtained by conjoint polymerization of a vinyl monomer, such as vinyl acetate, with varying amounts of unsaturated esters of IO-hendecenoic acid are insoluble, infusible products ranging in physical appearance from hard, glass-like resins to soft crumbly gels. The copolymers formed from mixtures of vinyl acetate with vinyl, allyl, or methallyl IO-hendecenoate, wherein the amount of the alkenyl ester of hendecenoic acid exceeds 20 to 30 percent, by weight, of the monomer mixture, are soft, insoluble products whereas tough elastic insoluble vinyl acetate copolymers are obtained from mixtures containing as much as about 50 percent, by weight, of 2-chloroallyl IO-hendecenoate.

The esters of this invention are thus useful for various purposes in the production of synthetic plastics and similar compositions. They can be utilized in the preparation of insoluble resinous materials by copolymerization with other monomers which polymerize to give soluble products. The alkenyl esters which, as such, do not readily undergo polymerization, like the methylallyl hendecenoates, are also adapted for use as: plasticizers and modifying agents. Chloroalkenyl esters, like chloroallyl hendecenoates, are suitable for the production of a wide range of copolymers and impart superior properties to the resulting products.

The following examples invention:

EXAMPLE I Preparation of vinyl IO-hendecenoate Eightv-three grams (0.45 mole) of IO-hendecenoic acid, M. P. 24.324.5 C. and neutralization equivalent 185, was dissolved in 232 grams (2.70 moles) of freshly distilled vinyl acetate, B. P. 73 C., and 1.7 grams of mercuric acetate and 0.15 ml. of 100% sulfuric acid were added. The soluare illustrative of the 3 tion was refluxed for three hours in an atmosphere of nitrogen and the sulfuric acid was then neutralized by the addition of sodium acetate.

' Excess vinyl acetate was recovered by distillation at atmospheric pressure and the distillation was then completed at about mm. pressure. Vinyl IO-hendecenoate was obtained in about 70% yield as a colorless liquid which on redistillation had the following characteristics:

i B. P 124-l24.5 C./10 mm.

1.4442 d4" 0.8799 Molecular refraction 63.5 (calcd. 63.0) Iodine number 238 (calcd. 241) EXAMPLE 11 Preparation of allyl JO-hendecenoate Seventy-four grams (0.4 mole) of 10-hendecenolc acid, 43.5 grams (0.8 mole) of allyl alcohol, 1.5 grams naphthalene-2-sulfonic acid and 250 ml. of benzene were refluxed for five hours. The water formed during the reaction was removed azeotropically with the benzene, and the benzene was returned continuously to the reaction mixture. The acid catalyst was then neutralized by the addition of sodium bicarbonate. The benzene was recovered by distillation at atmospheric pressure and the unreacted allyl alcohol was distilled of! at 100 mm. The pressure was then re-, duced to 50 min. and allyl IO-hendecenoate was obtained in about 90% yield as a colorless liquid, which on redistillation had the following characteristics:

B. P 179.5480 C./50 mm.

Molecular refraction 67.9 (calcd. 67.6)

Iodine number 227 (calcd. 226) Saponiflcation equivalent 225 (calcd. 224) EXAMPLE III Preparation of Z-chloroallyl ZO-hendecenoate 2-chloroallyl 10-hendecenoate was prepared as described in Example II from 74 grams (0.4 mole) of IO-hendecenoic acid, 74 grams (0.8 mole) of 2-chloroallyl alcohol, 1.5 grams of naphthalene- 2-sulfonic acid and 250 ml. of benzene. It was obtained in 90% yield as a colorless liquid which on redistillation had the following characteristics:

B. P. 144.5-145.5 C./4.5 mm.

Molecular refraction 72.5 (calcd. 72.4)

EXAMPLE IV Preparation of crotyl 1 O-hendecenoate Crotyl IO-hendecenoate was prepared as described in Example II, using 74 grams (0.4 mole) of 10-hendecenoic acid, 58 grams (0.8 mole) of crotyl alcohol, 1.5 grams of naphthalene-2-sulfonic acid and 250 ml. benzene. The ester was obtained in about 90% yield as a colorless liquid which on redistillation had the following characteristics:

B. P 157158 C./10.5 mm.

Molecular refraction 72.7 (calcd. 72.2) Iodine number 212 (calcd. 213) Saponiflcation equivalent 241 (calcd. 238) 4 EXAMPLEV Preparation of I-methylally IO-hendecenoate l-methylallyl lo-hendecenoate was prepared as described in Example II, using 74 grams (0.4 mole) of lo-hendecenoic acid, 58 grams (0.8 mole) of 3-buten-2-o1 (methyl vinyl carbinol), 1.5 grams naphthalene-2-sulfonic acid and 250 ml. benzene. The reaction mixture was refluxed for 24 hours. The ester was obtained in about yield as a colorless liquid which on redistillation had the following characteristics:

B. l. 145146 C./11 mm. n 1.4417

Molecular refraction 72.6 (calcd. 72.2) Iodine number 212 (calcd. 213) Saponification equivalent 241 (calcd. 238) EXAMPLE VI Preparation of Z-methyZaZZyl lo-hendec'enoate A freshly cut piece of metallic sodium weighing 0.35 gram was dissolved in 126 grams (1.75. moles) of methylallyl alcohol, and 69 grams (0.35 mole) of methyl 10-hendecenoate (prepared from 10-hendecenoic acid by esterification with anhydrous methanol, sulfuric acid being employed as catalyst) was added. The solution was heated on the steam bath (95-99 C.) for five hours in an atmosphere of nitrogen, and excess methylallyl alcohol was then recovered by distillation at mm. pressure. The distillation was then completed at about 10 mm. pressure and 2-methylallyl 10- hendecenoate was obtained in about 70% yield as a colorless liquid which on redistillation had the following characteristics:

B. P. 15l-152 C./10 mm. 11 1.4467

Molecular refraction 72.4 (calcd. 72.2) Iodine number 214 (calcd. 213) Saponification equivalent 239 (calcd. 238) EXAMPLE VII Preparation of furfuryl 10-hendecenoate Furfuryl lo-hendecenoate was prepared as described in Example VI, using 172 grams (1.75 moles) of furfuryl alcohol, 69 grams (0.35 mole) of methyl 10-hendecenoate and 0.35 gram of sodium. Unreacted furfuryl alcohol was distilled off at 50 mm. and furfuryl IO-hendecenoate was obtained as a pale yellow liquid which on redistillation had the following characteristics:

B. P. l64-l65 c./4.3 mm. 11 1.4671

Molecular refraction 75.8 (calcd. 75.8)

Saponiflcation equivalent 261 (calcd. 264) EXAMPLE VIII Mixtures of vinyl acetate with vinyl lO-hendecenoate, allyl IO-hendecenoate, methylallyl IO-hendecenoate and 2-rchloroallyl 10-hendecenoate, respectively, to each of which 0.5% by weight of benzoyl peroxide was added, were copolymerized by the procedure described by Guile and Huston, Laboratory Manual of Synthetic Plastics and Resinous Materials 1944, p. 99. The composition of the monomer mixtures aware it e used and the physical properties or the resulting REFERENCES mm copolymerization products are shown in the fol- The following references are of record in the lowing table: file 01' this patent:

Composition of Monomer Mixture (in ports weight) by Polymerizate Aoe- Ester ubil- Physical Appearance Hard, glasslike, colorless. Tongs-hard, colorless. Tou h, elastic, colorless. Bolt, c 'umbly, colorless.

0 Vhiyl IO-Heudecenoalo:

Tou h, hard, colorless.

Tough, elastic, colorless. Bolt, colorless. Soft, crumbly, colorless.

Tough, hard, colorless.

Tough, elastic, colorless.

l ess.

soft. co orl Soft, easily torn, colorless.

HHHHH HHHHH P IHHHH Tough, hard, colorless.

o. Tough, elastic, colorless.

o. Tough elastic, pale yellow. Soft, crumbly, pale yellow.

sea-ass asses sass: eases Hl-lHl-QHH S-Soluble at room temperature in acetone, amyl acetate and acetic acid.

llalns gluble in boiling acetone and benzene, and in my] acetate and acetic acid s Analogous results are obtained if the poly- UNITED STATES PATENTS merization is conducted using other organic pe- I roxides or similar polymerization catalyst, such fig g s a1 g i pefgulmes and the like in place benmyl 2 299 862 Toussaint et 51 Oct 27' 1942 perox e. Having thus described our invention, we 3 2; 55 1- claim:

I 2,374.0 17, 1945 A copolymer of vinyl acetate and 2-chloroallyl 2 475 233 et a1 fi 5 1949 IO-hendecenoate, sai copolymer containin about from 1 to 50 percent, by weight, of said 2- FOR N A T chlorallyl IO-hendecenoate. Number Country t DANIEL RN 581,501 Great Britain Oct. 15, 1946 ED UND F. JOR DAN. JR. 846,063 ran May 2'1, 1939 

